JP5565695B2 - Method for producing colored resin particles - Google Patents

Description

The present invention relates to a method for producing colored toner fine particles, which can be used as a toner for developing an electrostatic latent image in electrophotography and the like, and has a low environmental load on resin fine particles attached to the surface.
Further, the present invention relates to a method for producing a colored toner fine particle, which can be used in electronic paper and has resin fine particles attached to its surface, with a low environmental load.

  In an electrophotographic image forming apparatus, colored resin particles containing a colorant are used as a toner to form a visible image. Colored resin particles are also used for image formation for electronic paper.

Among various toners, there are polymerized toners having a small particle size and a narrow particle size distribution.
Furthermore, as a toner manufacturing method that can use polyester having excellent fixability as a binder resin as a main component, an oil phase in which at least a binder resin such as polyester and a colorant are dissolved or dispersed in an organic solvent is prepared. The oil phase is dispersed in an aqueous phase containing at least a surfactant and dispersed in the aqueous phase, and then the organic solvent is removed from the system and the resulting resin particles are washed. There is a method of obtaining toner by drying (hereinafter referred to as dissolution suspension method).

However, a toner having polyester as a main component of a binder resin as in the above-described dissolution suspension method tends to be less easily charged than a toner having a styrene acrylic resin as a main component. Particularly in a one-component development system, toner is removed by stirring or rubbing between a supply member such as a supply roller and a developer carrier such as a development roller, or by rubbing between a developer carrier and a regulation member such as a regulation blade. Although charging is performed, the toner has fewer opportunities to be charged compared to a method called a two-component development system in which the toner is charged by stirring and mixing with a carrier such as iron powder, so that the low charging property is a greater problem. .
Also, when used for image formation of electronic paper, in addition to the uniformity of the particle size distribution of the colored resin particles, the fluidity of the particles is necessary, but the coloring obtained in an aqueous system such as the dissolution suspension method Resin particles have poor fluidity and are not suitable for image formation of electronic paper.

For this reason, various studies have been made. As one of the methods, there is known a method in which a vinyl resin having excellent chargeability is present on the toner surface.
Among them, for example, in Patent Document 1, a vinyl resin fine particle dispersion is coexisted in an aqueous phase, and an oil phase is dispersed in the aqueous phase to produce oil droplets. A method of forming a layer is described. The described vinyl resins have many carboxyl groups derived from methacrylic acid, and are considered to have a protective colloidal function that assists the dispersibility of the oil phase droplets. As a result, it is thought that the resin layer of vinyl resin can be uniformly formed on the surface of the oil phase droplets. However, since there are many carboxyl groups, the hygroscopicity of the toner surface is increased, so the chargeability is improved The effect was not always sufficient, and it did not have satisfactory charging performance particularly in a high temperature and high humidity environment. In addition, in the production method described in this document, when attempting to form a shell structure with a vinyl-based resin with a reduced amount of carboxyl groups, the dispersion stability of the oil phase droplets is reduced, resulting in coarse particles. As a result, particles satisfactory as a toner could not be obtained.

Patent Document 2 discloses that an oil phase is dispersed in an aqueous phase to produce oil droplets, and then a vinyl resin fine particle dispersion is added before and after removing the solvent from the obtained oil droplet dispersion, Describes a method in which a vinyl-based resin is present on the surface of particles from which oil droplets or solvent have been removed by performing the above. In this method, heating is performed at a high temperature of 70 ° C. or higher in order to securely attach the vinyl resin to the core particles, but a great deal of energy is required for actual industrial production. However, it is not a preferable method from the viewpoint of economy and environmental load.
Further, Patent Document 3 describes the following in the production of core-shell type resin particles.
In the description of the present invention, the resin having a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium base when producing an aqueous dispersion (generally basic) When the molecular weight per functional group is preferably 1,000 or less), the higher the pH of the aqueous medium, the higher the coverage. Conversely, it is stated that the lower the pH, the lower the coverage. Although it is possible to adjust the pH with a water-soluble amine compound as described in the above-mentioned document, the toner produced using this compound has poor adhesion of resin fine particles on the surface of the core particles, and furthermore, the charging performance is extremely low. In some cases, the electrophotographic process may have problems due to poor charging. Moreover, in the thing of patent document 3, although the resin fine particle used as a shell agent is added at the time of emulsification, when a shell agent is added at the time of emulsification, many will be taken in in a core, and it will be in the core surface. It is difficult to uniformly disperse resin fine particles.

Originally, in the production of a granulated toner, a polyester resin, a polyamine compound, and an oil phase in which other materials (coloring agent, release agent, charge control agent, viscosity modifier, etc.) are dissolved and dispersed in an organic solvent Prepare an aqueous phase containing a polymer dispersant such as a low molecular weight activator or organic resin fine particles. Then, the oil phase and the aqueous phase are mixed and stirred (emulsification step), and the oil phase is dispersed in the aqueous phase, whereby the oil phase particles are granulated to obtain toner particles. However, when new resin fine particles are adhered to the surface layer of the granulated toner particles, if the polyamine compound is contained, the adhesion to the particle surface layer becomes non-uniform and the surface does not adhere uniformly to the surface. It was.
In addition, when a vinyl resin is introduced in a state where the solvent is not removed, when a vinyl resin having a small polar group such as a carboxyl group is used, the dispersion stability of the oil droplets is lowered, so that the oil droplets are aggregated. Together, it was not possible to obtain satisfactory particles as a toner.

  The present invention is capable of efficiently adhering resin fine particles to the particle surface, and producing colored resin fine particles that can be suitably used as an electrostatic latent image developing toner for electrophotography and as colored particles for electronic paper. It aims at providing the manufacturing method which can manufacture with little load.

As a result of extensive studies by the present inventors, a step of preparing an oil phase in which at least a resin and a colorant are dissolved or dispersed in an organic solvent, an aqueous phase having at least an inorganic base and a surfactant in an aqueous medium. A step of producing, a step of dispersing the oil phase in the aqueous phase to produce a dispersion in which core particles made of the oil phase are dispersed, and a resin fine particle dispersion is charged into the dispersion to put the dispersion on the core particles In the method for producing colored resin particles including at least the step of adhering the fine particles, a resin is applied to the particle surface by selecting the amount of the inorganic base within a suitable range in place of the polyamine compound that has been excellent in granulating properties. It has been found that colored resin particles can be efficiently attached, and colored resin particles that can be suitably used as an electrostatic latent image developing toner for electrophotography can be produced with a reduced environmental burden. It came to that.
That is, the present invention is as described below.

(1) a step of producing an oil phase in which at least a resin and a colorant are dissolved or dispersed in an organic solvent;
Producing an aqueous phase having at least a surfactant in an aqueous medium;
A step of dispersing the oil phase in the aqueous phase to produce a colored particle dispersion to produce core particles;
Adding at least resin fine particles to the colored particle dispersion in which the core particles are formed, and attaching the resin fine particles to the surface of the core particles;
Removing the solvent to obtain colored resin particles;
Washing the colored resin particles;
In the method for producing colored resin particles including at least a step of drying the colored resin particles, an inorganic base is dissolved in the colored particle dispersion to be alkaline, and a heating step is performed in the step of attaching the resin fine particles. A method for producing colored resin particles, characterized by not passing through .
(2) Production of colored resin particles according to (1), wherein the inorganic base is added in a step of producing the aqueous phase or a step of producing an oil phase in which the colorant is dissolved or dispersed. Method.
(3) The method for producing colored resin particles according to (1) or (2), wherein the resin fine particles have a volume average particle diameter of 60 to 120 nm.
(4) The method for producing colored resin particles according to any one of (1) to (3), wherein the washing step is a washing treatment with an acid.
(5) The method for producing colored resin particles according to any one of (1) to (4), wherein the acid value of the resin is 2 to 26 mgKOH / g.
(6) The method for producing colored resin particles according to any one of (1) to (5), wherein the resin is a polyester resin.
(7) The method for producing colored resin particles according to any one of (1) to (6), wherein a modified resin having an isocyanate group at a terminal is dissolved in the oil phase.
(8) The method for producing colored resin particles according to (7), wherein the modified resin has a polyester skeleton.
(9) The method for producing colored resin particles according to any one of (1) to (8), wherein the resin fine particles are made of a vinyl resin.
(10) The method for producing colored resin particles according to (9), wherein the styrene monomer contained in the vinyl resin is 80% by weight or more.
(11) The method for producing colored resin particles according to (10), wherein a styrene monomer contained in the vinyl resin is 90% by weight or more.
(12) The method for producing colored resin particles according to any one of (1) to (11), wherein the colored resin particles do not contain an amine compound having an active hydrogen group.

  According to the method for producing the colored resin particles of the present invention, the electrostatic latent image development can efficiently and uniformly adhere the resin fine particles onto the core particles without going through the heating step, and has excellent charging stability. Planting tree particles suitable for image formation of toner for use and electronic paper can be obtained.

1 is a schematic cross-sectional view illustrating an example of a configuration of an image forming apparatus according to an embodiment of the present invention. It is a schematic sectional drawing which shows the structure of the image formation part which arrange | positions a photoreceptor. It is a schematic sectional drawing which shows the structure of a developing device. It is a schematic sectional drawing which shows the structure of a process cartridge.

Hereinafter, the present invention will be described in detail.
<Resin fine particles to be adhered to the core particle surface>
Typical resin fine particles used in the present invention include a polyester resin or a vinyl resin obtained by polymerizing a monomer mixture comprising at least a styrene monomer or a hybrid resin having a vinyl resin component in a polyester resin skeleton. A vinyl resin is preferable in consideration of compatibility with the wax dispersed in the vicinity of the toner surface layer.
More specifically, in order to use the colored resin particles obtained in the present invention as particles that function by charging such as toner for developing an electrostatic latent image, the surface of the colored resin particles has a structure that is easily charged. For this purpose, a styrenic monomer having an electron orbit such that an electron can stably exist like an aromatic ring structure is 50 to 100% by weight, preferably 80 to 100% by weight, more preferably 95% of the monomer mixture. It is good to use ~ 100% by weight. When the styrene monomer is less than 50% by weight, the chargeability of the obtained colored resin particles becomes poor, and the application of the colored resin particles is limited.

Further, when adding the resin fine particles, what is important is the average particle diameter of the resin fine particles.
In the present invention, when the resin fine particles are added to the surface of the core particles, the volume average particle diameter of the resin fine particles is controlled to 60 to 120 nm, preferably 60 to 110 nm, and more preferably 60 to 100 nm. When the particle diameter of the resin fine particles is larger than 120 nm, the ratio of forming the particles with only the resin fine particles increases when forming the particles, and as a result, the uniformity of the resin fine particles dispersed on the surface of the core particles is lowered. On the other hand, if it is smaller than 60 nm, the cohesiveness of the resin fine particles alone is reduced, the ratio of floating particles not adhering to the core particle surface is increased, and as a result, the uniformity of the resin fine particles dispersed on the core particle surface is reduced.
Therefore, in the present invention, as a means for uniformly dispersing the resin fine particles on the surface of the core particles, the resin fine particles are controlled to have an arbitrary particle size in parallel with using an inorganic base instead of the amine compound. The resin particles can be uniformly dispersed on the particle surface.

Here, the styrene monomer refers to an aromatic compound having a vinyl polymerizable functional group. Examples of the polymerizable functional group include a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryloyl group.
Specific examples of the styrene monomer include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-carboxystyrene, and metal salts thereof. 4-styrenesulfonic acid or a metal salt thereof, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, and the like.
Of these, it is preferable to mainly use styrene which is easily available, has excellent reactivity and high chargeability.

  In the vinyl resin suitably used in the present invention, the acid monomer should be used in an amount of 0 to 7% by weight of the monomer mixture, preferably 0 to 4% by weight, and more preferably no acid monomer is used. Is good. When the acid monomer is used in an amount exceeding 7% by weight, the resulting vinyl resin fine particles have high dispersion stability, so that such a vinyl resin is contained in a dispersion in which oil droplets are dispersed in an aqueous phase. Even if resin fine particles are added, they are difficult to adhere at room temperature or are easily detached even if they are attached, and they are easily removed in the process of solvent removal, washing, drying, and external addition treatment. Furthermore, by making the usage-amount of an acid monomer 4 weight% or less, a change in charging property can be reduced depending on the environment in which the obtained colored resin particles are used.

Here, the acid monomer means a compound having a vinyl polymerizable functional group and an acid group, and examples of the acid group include carboxylic acid, sulfonyl acid, and phosphonic acid.
Examples of the acid monomer include carboxyl group-containing vinyl monomers and salts thereof ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, itaconic acid mono Alkyl, itaconic acid glycol monoether, citraconic acid, monoalkyl citraconic acid, cinnamic acid, etc.), sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, phosphate group-containing vinyl monomers and salts thereof, etc. There is. Of these, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, and monoalkyl fumarate are preferred.

Although it does not specifically limit as a method of obtaining vinyl resin fine particles, The following (a)-(f) is mentioned.
(A) The monomer mixture is reacted by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method to produce a dispersion of vinyl resin fine particles.
(B) The monomer mixture is polymerized in advance, and the resin obtained is pulverized using a mechanical pulverizer or jet pulverizer and then classified to produce resin fine particles.
(C) Resin fine particles are produced by polymerizing the monomer mixture in advance and spraying the resulting resin solution in a solvent in the form of a mist.
(D) polymerizing the monomer mixture in advance, adding a solvent to the resin solution obtained by dissolving the obtained resin in a solvent, or cooling the resin solution previously dissolved in a solvent to precipitate resin fine particles; Resin fine particles are produced by removing the solvent.
(E) A monomer solution is polymerized in advance, and a resin solution obtained by dissolving the obtained resin in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and the solvent is removed by heating or decompression.
(F) A monomer mixture is polymerized in advance, an appropriate emulsifier is dissolved in a resin solution obtained by dissolving the obtained resin in a solvent, and water is added to perform phase inversion emulsification.

Among them, the method (a) is preferable because it is easy to produce and the resin fine particles can be obtained as a dispersion, and can be smoothly applied to the next step.
In the method (a), when the polymerization reaction is performed, a dispersion stabilizer is added to the aqueous medium, or the dispersion stability of the resin fine particles obtained by polymerization can be imparted to the monomer that performs the polymerization reaction. It is preferable to add a stable monomer (so-called reactive emulsifier) or to use these two means in combination to impart dispersion stability of the resulting vinyl resin fine particles. If a dispersion stabilizer or reactive emulsifier is not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the dispersion stability of the obtained resin fine particles is low, so that the storage stability Colored resin particles finally obtained because the core particles are easily agglomerated and united because they are agglomerated during storage or because the dispersion stability of the particles in the resin fine particle adhesion process described later decreases. This is not preferable because the uniformity of the particle size, shape, surface, and the like of the resin deteriorates.

  Examples of the dispersion stabilizer include surfactants and inorganic dispersants. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, and alkylamine salts. Amine salt types such as amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N Amphoteric surfactants such as N- dimethyl ammonium betaine and the like. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.

In the case of producing the resin fine particles of the present invention, a generally used chain transfer agent can be used for the purpose of adjusting the molecular weight. The chain transfer agent is not particularly limited, but an alkyl mercaptan chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is preferably used. The alkyl mercaptan-based hydrophobic chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is not particularly limited, but butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl Mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl ester of mercaptopropionate, 2-mercaptoethyl ester of octanoate, 1,8-dimercapto-3,6- Dioxaoctane, decane trithiol, dodecyl mercaptan and the like can be mentioned. In this case, the hydrophobic chain transfer agent may be used alone or in the form of a mixture of two or more.
At this time, the addition amount of the chain transfer agent is not particularly limited as long as the obtained copolymer can be adjusted so as to have a desired molecular weight, but is preferably 0 with respect to the total moles of the monomer components. 0.01 to 30 parts by mass, more preferably 0.1 to 25 parts by mass. At this time, if the added amount of the chain transfer agent is less than 0.01 parts by mass, the molecular weight of the resulting copolymer becomes too large, so that the fixability is lowered or gelation occurs during the polymerization reaction. there is a possibility. On the contrary, when the addition amount of the chain transfer agent exceeds 30 parts by mass, the chain transfer agent remains in an unreacted state, and the molecular weight of the obtained copolymer is small, causing member contamination.

<Resin added to organic solvent>
As the resin to be added to the organic solvent, a resin that at least partially dissolves in the organic solvent is used, but the acid value is preferably 2 to 26 mgKOH / g. When the acid value exceeds 26 mgKOH / g, the transition to the aqueous phase is likely to occur, and as a result, loss in the material balance occurs during the production process, or the dispersion stability of the oil droplets deteriorates. Problems are likely to occur. On the other hand, when the acid value is less than 2 mgKOH / g, the polarity of the resin becomes low, and it becomes difficult to uniformly disperse the colorant having a certain degree of polarity in the oil droplets.

The type of resin is not particularly limited, but when used as an electrostatic latent image developing toner in electrophotography, it is preferable to use a resin having a polyester skeleton because good fixability can be obtained. Examples of the resin having a polyester skeleton include a polyester resin and a block polymer of a polyester and a resin having another skeleton, and the use of the polyester resin is preferable because the uniformity of the colored resin particles obtained is high.
Examples of the polyester resin include ring-opening polymers of lactones, polycondensation products of hydroxycarboxylic acids, polycondensates of polyols and polycarboxylic acids, and the like. Polycondensates are preferred.
The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, the heat-resistant storage stability is deteriorated, and if it exceeds 30000, the low-temperature fixability as an electrostatic latent image developing toner is deteriorated.

The polyol and carboxylic acid for producing the polyester resin will be described below.
(Polyol)
Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2), (1-1) alone or (1-1) and a small amount of (1-2). Mixtures are preferred.
Examples of the diol (1-1) include the following.
Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.);
Alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.);
Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; 3,3′-difluoro-4,4′-dihydroxybiphenyl 4,4'-dihydroxybiphenyls such as bis (3-fluoro-4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2- Bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) ) -1,1,1,3,3,3-hexafluoropropyl Bis bread etc. (hydroxyphenyl) alkanes, bis (3-fluoro-4-hydroxyphenyl) bis (4-hydroxyphenyl) such as ethers ethers;
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols

  Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

Examples of the trivalent or higher polyol (1-2) include the following.
3 to 8 or more polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.);
Trivalent or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.);
Alkylene oxide adducts of the above trivalent or higher polyphenols

(Polycarboxylic acid)
Examples of polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone or (2-1) and a small amount of ( The mixture of 2-2) is preferred.

  Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalenedicarboxylic acid, etc.), 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid 5-trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 3,3'-bis (trifluoromethyl Le) -4,4'-biphenyl dicarboxylic acid, 2,2'-bis (trifluoromethyl) -3,3'-biphenyl dicarboxylic acid, and the like hexafluoroisopropylidene diphthalic anhydride. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

(Modified resin)
In addition, in the oil phase, in order to increase the mechanical strength of the colored resin particles obtained, or to prevent high-temperature offset during fixing in addition to the previous mechanical strength when used as a toner for developing an electrostatic latent image. Alternatively, a colored resin particle may be obtained by dissolving a modified resin having an isocyanate group at the terminal. As a method for obtaining a modified resin, a method for obtaining a resin having an isocyanate group by polymerizing with an isocyanate-containing monomer, a method for obtaining a resin having an active hydrogen at the terminal, and then reacting with a polyisocyanate. Although the method of introduce | transducing an isocyanate group into a polymer terminal etc. is mentioned, The latter method can be preferably employ | adopted from the controllability of introducing an isocyanate group into a terminal. Examples of the active hydrogen include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferable. As the skeleton of the modified resin, in consideration of the uniformity of the particles, it is preferable to use the same resin as that dissolved in the organic solvent, and it is preferable to have a polyester skeleton. As a method for obtaining a resin having an alcoholic hydroxyl group at the end of the polyester, in the polycondensation of the polyol and the polycarboxylic acid, the polycondensation reaction may be carried out by making the number of functional groups of the polyol larger than the number of functional groups of the polycarboxylic acid. .

<Inorganic base>
As the inorganic base used for the purpose of adjusting the hydrogen ion concentration index of the system in the core particle production step, a known inorganic base can be used. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide; lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, carbonate Carbonates such as calcium; hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate; ammonia solutions, and any mixtures thereof. The inorganic base may be used in either the oil phase or the aqueous phase. Even by adding an inorganic base to the oil phase, the resin phase, which is a toner component, is preliminarily permeated to improve the uniformity of the particles. It is possible to improve the fineness of the resin fine particles. By using an inorganic base in the aqueous phase, the pH in the aqueous phase can be controlled to be alkaline, and fine adjustment of particle size control during emulsification becomes possible. In addition, also when adding an inorganic base at the time of oil phase preparation, when mixing a water phase and an oil phase, the effect substantially equivalent to the above is acquired. Although the pH can be adjusted by using a water-soluble organic amine compound, the toner produced using this has poor adhesion of resin fine particles on the surface of the core particle, and furthermore, the charging performance is remarkably low. Since it becomes very difficult to use, it is not preferable.
The organic amine compound here is an amine compound having an N—C bond, and triethylamine, isophoronediamine, ethanolamine and the like are included in the organic amine compound.

<Organic solvent>
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. When the resin to be dissolved or dispersed in an organic solvent is a resin having a polyester skeleton, it is better to use an ester solvent such as methyl acetate, ethyl acetate or butyl acetate or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone. Among them, methyl acetate, ethyl acetate, and methyl ethyl ketone, which have high solvent removal properties, are particularly preferable.

<Aqueous medium>
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

<Surfactant>
A surfactant is used to produce droplets by dispersing the oil phase in an aqueous medium.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is. Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.

  Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms, and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. Further, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

<Inorganic dispersant>
The dissolved or dispersed toner composition may be dispersed in the aqueous medium in the presence of an inorganic dispersant or resin fine particles. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

<Protective colloid>
Further, the dispersed droplets may be stabilized by a polymer protective colloid.
For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, eg acetic acid Vinyl, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant may remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

<Colorant>
As the coloring agent of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fayce Red, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used.

<Colorant masterbatch>
The colorant used in the present invention can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

<Master batch production method>
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of colorant is mixed and kneaded with resin and organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

Further, further stabilization of the dispersed droplets may be promoted by adding the following water-soluble polymer.
Examples of the water-soluble polymer include cellulosic compounds (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan, Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid, Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
<Release agent>
Further, when the colored resin particles are used as a toner for developing an electrostatic latent image, a release agent may be dispersed in an organic solvent for the purpose of improving fixing releasability.
As the mold release agent, a material such as wax or silicone oil, which has a sufficiently low viscosity when heated in the fixing process and is difficult to be compatible or swelled with other materials of the colored resin particles and the surface of the fixing member is used. Considering the storage stability of the colored resin particles themselves, it is preferable to use a wax that exists as a solid in the colored resin particles during normal storage.

Examples of waxes include long-chain hydrocarbons and carbonyl group-containing waxes. Examples of long-chain hydrocarbons include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); petroleum waxes (paraffin wax, sazol wax, microcrystalline wax, etc.) In addition to Fischer-Tropsch wax.
Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) ); And dialkyl ketones (such as distearyl ketone).
Of these, long-chain hydrocarbons having particularly good releasability are preferred. Furthermore, when a long chain hydrocarbon is used as a release agent, a carbonyl group-containing wax may be used in combination.

<Charge control agent>
Furthermore, the charge control agent may be dissolved or dispersed in an organic solvent as necessary.
All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

<Manufacturing method>
Next, the manufacturing process will be described.
(Oil phase preparation process)
As a method of preparing an oil phase in which a resin, a colorant or the like is dissolved or dispersed in an organic solvent, the resin, the colorant, or the like is gradually added to the organic solvent while stirring, and the oil phase can be dissolved or dispersed. That's fine. However, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles should be made smaller prior to addition to the organic solvent. It is preferable.
As described above, the master batch of the colorant is one of the means, and the same method can be applied to the release agent and the charge control agent.

As another means, it is also possible to add a dispersion aid as necessary in an organic solvent and disperse the colorant, release agent, and charge control agent in a wet manner to obtain a wet master.
As another means, if a material that melts below the boiling point of the organic solvent is dispersed, a dispersion aid is added in the organic solvent as necessary, and the mixture is heated with stirring with the dispersoid. After dissolution, crystallization may be performed by cooling with stirring or shearing to produce dispersoid microcrystals.

  The colorant, release agent, and charge control agent dispersed using the above means may be further dispersed after being dissolved or dispersed together with the resin in the organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

(Core particle production process)
The method for producing a dispersion in which the oil phase obtained in the above-described step is dispersed in an aqueous medium having at least a surfactant and core particles composed of the oil phase are dispersed is not particularly limited. Known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 10000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 1 to 5 minutes. If the dispersion is performed for more than 5 minutes, particles having an undesirably small diameter may remain, or the dispersion may be overdispersed, resulting in instability of the system and generation of aggregates and coarse particles. It is not preferable. Conversely, if it is shorter than 1 minute, the uniformity of the particles is poor and it is difficult to obtain a desired distribution. As temperature at the time of dispersion | distribution, it is 0-40 degreeC normally, Preferably it is 10-30 degreeC. If it exceeds 40 ° C., the molecular motion becomes active, so that the dispersion stability is lowered and aggregates and coarse particles are easily generated, which is not preferable. On the other hand, when the temperature is less than 0 ° C., the viscosity of the dispersion increases, and the shear energy required for dispersion increases, so that the production efficiency decreases.

(Resin fine particle adhesion process)
The obtained core particle dispersion can keep the core particle droplets stably while stirring. In this state, the above-mentioned resin fine particle dispersion is charged and adhered onto the core particles. The resin fine particle dispersion is preferably charged over 30 seconds. When the charging is performed in less than 30 seconds, the dispersion system is rapidly changed, so that agglomerated particles are generated and the adhesion of resin fine particles is not uniform. On the other hand, it is not preferable from the viewpoint of production efficiency to add to the dark cloud for a long time, for example, exceeding 60 minutes.

  The resin fine particle dispersion may be diluted or concentrated to adjust the concentration as appropriate before being added to the core particle dispersion. The concentration of the resin fine particle dispersion is preferably 5 to 30% by weight, and more preferably 8 to 20% by weight. If it is less than 5%, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and the adhesion of the resin fine particles becomes insufficient. On the other hand, if it exceeds 30% by weight, the resin fine particles are likely to be unevenly distributed in the core particle dispersion, and as a result, the adhesion of the resin fine particles becomes non-uniform.

  The reason why the resin fine particles adhere to the core particles with sufficient strength by the method of the present invention is that when the resin fine particles adhere to the droplets of the core particles, the core particles can freely deform and come into contact with the resin fine particle interface. This is probably because the surface is sufficiently formed, and the resin fine particles are swollen or dissolved by the organic solvent, and the resin fine particles and the resin in the core particles are likely to adhere to each other. Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, in the state of the core particle dispersion, it is 50 wt% to 150 wt%, preferably 70 wt% based on the solid content (resin, colorant, and if necessary, release agent, charge control agent, etc.). It should be in the range of% to 125% by weight. If it exceeds 150% by weight, the amount of colored resin particles obtained in a single production process is reduced and the production efficiency is low, and if there is a large amount of organic solvent, the dispersion stability is lowered and stable production becomes difficult. .

  The temperature at which the resin fine particles adhere to the core particles is 10 to 60 ° C, preferably 20 to 45 ° C. When the temperature exceeds 60 ° C., the energy required for production increases, so that the environmental burden on the production increases. In addition, resin particles with low acid value may be present on the droplet surface, resulting in unstable dispersion and coarse particles. May occur, which is not preferable. On the other hand, when the temperature is lower than 10 ° C., the viscosity of the dispersion is increased, and adhesion of resin fine particles becomes insufficient, which is not preferable.

(Demelting process)
In order to remove the organic solvent from the obtained colored resin dispersion, it is possible to employ a method in which the entire system is gradually heated while being stirred to completely evaporate and remove the organic solvent in the droplets.
Alternatively, the obtained colored resin dispersion can be sprayed into a dry atmosphere while stirring to completely remove the organic solvent in the droplets. Alternatively, the colored resin dispersion may be decompressed while stirring to evaporate and remove the organic solvent. The latter two means can be used in combination with the first means.
As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

(Aging process)
When a modified resin having an isocyanate group at the terminal is added, an aging step may be performed in order to advance the elongation / crosslinking reaction of the isocyanate. The aging time is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 65 ° C, preferably 35 to 50 ° C.

(Washing and drying process)
A known technique is used for washing and drying the toner particles dispersed in the aqueous medium.
That is, after solid-liquid separation with a centrifuge, a filter press or the like, the obtained toner cake is redispersed in ion-exchanged water at about room temperature to about 40 ° C. Furthermore, after removing impurities and surfactants by repeating the process of solid-liquid separation again several times, in the present invention, in order to disperse the inorganic base during the oil phase, the meaning of neutralizing the alkali component It is important to adjust the pH with an acid. After these treatments, the toner powder is obtained by drying with an air dryer, circulation dryer, vacuum dryer, vibration fluid dryer, or the like. At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

(External processing)
The obtained dried toner powder is mixed with different kinds of particles such as charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying a mechanical impact force to the mixed powder. It is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. Examples of the apparatus include Nobilta (manufactured by Hosokawa Micron Co., Ltd.), Meteole Inbo (manufactured by Nippon Pneumatic Co., Ltd.), and a hybridization system (manufactured by Nara Machinery Co., Ltd.).

The colored resin particles of the present invention can be used as a toner for developing an electrostatic latent image.
Hereinafter, an image forming method, an image forming apparatus, and a toner cartridge using the colored resin particles of the present invention as an electrostatic latent image developing toner will be described.

  The image forming apparatus of the present invention includes a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier that is exposed based on image data. Exposure means for writing an electrostatic latent image, developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it, and a visible image on the surface of the latent image carrier. The image forming apparatus includes at least a transfer unit that transfers to a transfer body and a fixing unit that fixes a visible image on the transfer body. Further, other units appropriately selected as necessary, for example, a charge eliminating unit and a cleaning unit , Recycling means, control means, etc.

  The image forming method of the present invention includes a charging step for uniformly charging the surface of the latent image carrier, an exposure step for exposing the surface of the charged latent image carrier based on image data, and writing an electrostatic latent image, A developer layer having a predetermined layer thickness is formed on the developer carrier by a developer layer regulating member, and the electrostatic latent image formed on the surface of the latent image carrier is developed through the developer layer to be visualized. An electrostatic latent image forming step comprising: a developing step, a transfer step for transferring a visible image on the surface of the latent image carrier to a transfer target, and a fixing step for fixing the visible image on the transfer target. And at least a development process, a transfer process, and a fixing process, and further include other processes appropriately selected as necessary, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like.

The electrostatic latent image can be formed, for example, by uniformly charging the surface of the latent image carrier with a charging unit and then exposing the surface of the latent image carrier imagewise with an exposure unit.
The visible image is formed by the development by forming a toner layer on a developing roller as a developer carrying member and transporting the toner layer on the developing roller so as to be in contact with a photosensitive drum as a latent image carrying member. Thus, the electrostatic latent image on the photosensitive drum is developed. The toner is stirred by the stirring means and mechanically supplied to the developer supply member. The toner supplied from the developer supply member and deposited on the developer carrier is formed into a uniform thin layer by passing through a developer layer regulating member provided to contact the surface of the developer carrier. Furthermore, it is charged. The electrostatic latent image formed on the latent image carrier is developed by attaching the toner charged by the developing means in the developing region to become a toner image.

The transfer of the visible image can be performed, for example, by charging the latent image carrier (photoconductor) using a transfer charger, and can be performed by the transfer unit.
The transferred visible image is fixed by using a fixing device to transfer the visible image transferred to the recording medium, and may be performed each time the toner of each color is transferred to the recording medium. On the other hand, it may be carried out simultaneously at the same time in a state of being laminated.

  There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.

  Next, the basic configuration of the image forming apparatus (printer) according to the embodiment of the present invention will be further described with reference to the drawings. FIG. 1 is a schematic diagram illustrating a configuration of an image forming apparatus according to an embodiment of the present invention. Here, an embodiment applied to an electrophotographic image forming apparatus will be described. The image forming apparatus includes yellow (hereinafter referred to as “Y”), cyan (hereinafter referred to as “C”), magenta (hereinafter referred to as “M”), black (hereinafter referred to as “K”). The color image is formed from the four color toners.

First, a basic configuration of an image forming apparatus (a “tandem type image forming apparatus”) that includes a plurality of latent image carriers and parallels the plurality of latent image carriers in the moving direction of the surface moving member will be described.
This image forming apparatus includes four photosensitive members 1Y, 1C, 1M, and 1K as latent image carriers. Although a drum-shaped photoconductor is taken as an example here, a belt-shaped photoconductor can also be adopted. Each of the photoconductors 1Y, 1C, 1M, and 1K is rotationally driven in the direction of the arrow in the drawing while being in contact with the intermediate transfer belt 10 that is a surface moving member. Each of the photoreceptors 1Y, 1C, 1M, and 1K is rotationally driven in the direction of the arrow in the drawing while being in contact with the intermediate transfer belt 10. Each of the photoreceptors 1Y, 1C, 1M, and 1K is obtained by forming a photosensitive layer on a relatively thin cylindrical conductive substrate and further forming a protective layer on the photosensitive layer. An intermediate layer may be provided between the protective layer.

  FIG. 2 is a schematic diagram showing the configuration of the image forming unit 2 in which the photoconductor is disposed. Since the configuration around each of the photoreceptors 1Y, 1C, 1M, and 1K in the image forming units 2Y, 2C, 2M, and 2K is the same, only one image forming unit 2 is illustrated, and a code Y for color coding is shown. , C, M, and K are omitted. Around the photosensitive member 1, along the surface movement direction, the charging device 3 as a charging unit, the developing device 5 as a developing unit, and the toner image on the photosensitive member 1 are transferred to a recording medium or an intermediate transfer member 10. A transfer device 6 as a transfer unit and a cleaning device 7 for removing untransferred toner on the photoreceptor 1 are arranged in this order. Between the charging device 3 and the developing device 5, light is emitted from an exposure device 4 as an exposure unit that performs exposure based on image data on the surface of the charged photoconductor 1 and writes an electrostatic latent image. Space is secured so that it can pass through.

The charging device 3 charges the surface of the photoreceptor 1 to a negative polarity. The charging device 3 according to the present embodiment includes a charging roller as a charging member that performs charging processing by a so-called contact / proximity charging method. In other words, the charging device 3 charges the surface of the photoreceptor 1 by bringing the charging roller into contact with or close to the surface of the photoreceptor 1 and applying a negative bias to the charging roller. A DC charging bias is applied to the charging roller such that the surface potential of the photoreceptor 1 is −500V.
Note that a charging bias in which an AC bias is superimposed on a DC bias can also be used. The charging device 3 may be provided with a cleaning brush for cleaning the surface of the charging roller. As the charging device 3, a thin film may be wound around both end portions in the axial direction on the peripheral surface of the charging roller and installed so as to contact the surface of the photoreceptor 1.
In this configuration, the surface of the charging roller and the surface of the photoreceptor 1 are extremely close to each other with a distance corresponding to the thickness of the film. Therefore, a discharge is generated between the surface of the charging roller and the surface of the photosensitive member 1 by the charging bias applied to the charging roller, and the surface of the photosensitive member 1 is charged by the discharge.
An electrostatic latent image corresponding to each color is formed on the surface of the photoreceptor 1 charged in this manner by exposure by the exposure device 4. The exposure device 4 writes an electrostatic latent image corresponding to each color on the photoreceptor 1 based on image information corresponding to each color. In addition, although the exposure apparatus 4 of this embodiment is a laser system, the other system which consists of an LED array and an imaging means can also be employ | adopted.

  The toner replenished into the developing device 5 from the toner bottles 31Y, 31C, 31M, and 31K is conveyed by the supply roller 5b and carried on the developing roller 5a. The developing roller 5 a is conveyed to a developing area facing the photoreceptor 1. Here, the developing roller 5 a moves in the same direction at a linear velocity faster than the surface of the photosensitive member 1 in a region facing the photosensitive member 1 (hereinafter referred to as “developing region”). Then, the toner on the developing roller 5 a supplies the toner to the surface of the photosensitive member 1 while rubbing the surface of the photosensitive member 1. At this time, a developing bias of −300 V is applied to the developing roller 5a from a power source (not shown), thereby forming a developing electric field in the developing region. Then, between the electrostatic latent image on the photoreceptor 1 and the developing roller 5a, an electrostatic force directed toward the electrostatic latent image side acts on the toner on the developing roller 5a. As a result, the toner on the developing roller 5 a adheres to the electrostatic latent image on the photoreceptor 1. By this adhesion, the electrostatic latent image on the photoreceptor 1 is developed into a corresponding color toner image.

The intermediate transfer belt 10 in the transfer device 6 is stretched around three support rollers 11, 12, and 13 and is configured to endlessly move in the direction of the arrow in the drawing. On the intermediate transfer belt 10, toner images on the photoreceptors 1Y, 1C, 1M, and 1K are transferred so as to overlap each other by an electrostatic transfer method. Although there is a configuration using a transfer charger in the electrostatic transfer system, a configuration using a transfer roller 14 that generates less transfer dust is adopted here. Specifically, primary transfer rollers 14Y, 14C, 14M, and 14K as transfer devices 6 are disposed on the back surface of the portion of the intermediate transfer belt 10 that contacts the photoreceptors 1Y, 1C, 1M, and 1K, respectively. Here, a primary transfer nip portion is formed by the portions of the intermediate transfer belt 10 pressed by the primary transfer rollers 14Y, 14C, 14M, and 14K and the photoreceptors 1Y, 1C, 1M, and 1K. When transferring the toner images on the photoreceptors 1Y, 1C, 1M, and 1K onto the intermediate transfer belt 10, a positive bias is applied to each primary transfer roller. As a result, a transfer electric field is formed in each primary transfer nip portion, and the toner images on the photoreceptors 1Y, 1C, 1M, and 1K are electrostatically attached to the intermediate transfer belt 10 and transferred.
A belt cleaning device 15 for removing toner remaining on the surface of the intermediate transfer belt 10 is provided around the intermediate transfer belt 10. The belt cleaning device 15 is configured to collect unnecessary toner adhering to the surface of the intermediate transfer belt 10 with a fur brush and a cleaning blade. The collected unnecessary toner is transported from the belt cleaning device 15 to a waste toner tank (not shown) by a transport means (not shown).

  Further, a secondary transfer roller 16 is disposed in contact with the portion of the intermediate transfer belt 10 stretched around the support roller 13. A secondary transfer nip portion is formed between the intermediate transfer belt 10 and the secondary transfer roller 16, and transfer paper as a recording member is fed into this portion at a predetermined timing. This transfer paper is accommodated in a paper feed cassette 20 on the lower side of the exposure apparatus 4 in the drawing, and is conveyed to the secondary transfer nip portion by a paper feed roller 21, a registration roller pair 22, and the like. Then, the toner images superimposed on the intermediate transfer belt 10 are collectively transferred onto the transfer paper at the secondary transfer nip portion. At the time of the secondary transfer, a positive bias is applied to the secondary transfer roller 16, and the toner image on the intermediate transfer belt 10 is transferred onto the transfer paper by a transfer electric field formed thereby.

  A heat fixing device 23 as a fixing unit is disposed downstream of the secondary transfer nip portion in the transfer paper conveyance direction. The heat fixing device 23 includes a heating roller 23a with a built-in heater and a pressure roller 23b for applying pressure. The transfer paper that has passed through the secondary transfer nip is sandwiched between these rollers and receives heat and pressure. As a result, the toner on the transfer paper is melted and the toner image is fixed on the transfer paper. Then, the fixed transfer paper is discharged by a paper discharge roller 24 onto a paper discharge tray on the upper surface of the apparatus.

  In the developing device 5, a developing roller 5a as a developer carrying member is partially exposed from an opening of the casing. Further, here, a one-component developer containing no carrier is used. The developing device 5 receives toner of the corresponding color from the toner bottles 31Y, 31C, 31M, and 31K shown in FIG. The toner bottles 31Y, 31C, 31M, and 31K are configured to be detachable from the main body of the image forming apparatus so that they can be replaced individually. With such a configuration, only the toner bottles 31Y, 31C, 31M, and 31K may be replaced at the time of toner end. Therefore, other components that have not yet reached the end of their life when the toner ends can be used as they are, and the user's expense can be reduced.

FIG. 3 is a schematic diagram illustrating the configuration of the developing device.
The developer (toner) in the developer container is agitated by a supply roller 5b as a developer supply member, and a developing roller 5a as a developer carrying member that carries the developer supplied to the photoreceptor 1 on the surface thereof. It is carried to the nip part. At this time, the supply roller 5b and the developing roller 5a are rotated in the reverse direction (counter rotation) at the nip portion. Further, the amount of toner on the developing roller 5a is regulated by a regulating blade 5c as a developer layer regulating member provided so as to come into contact with the developing roller 5a, and a thin toner layer is formed on the developing roller 5a. The toner is rubbed between the nip portion of the supply roller 5b and the developing roller 5a, the regulating blade 5c, and the developing roller 5a, and is controlled to an appropriate charge amount.

The developer of the present invention can be used in, for example, an image forming apparatus provided with a process cartridge as shown in FIG. In the present invention, a plurality of components such as an electrostatic latent image carrier, an electrostatic latent image charging unit, a developing unit, and an electrostatic latent image carrier are integrally coupled as a process cartridge. The process cartridge is configured to be detachable from the image forming apparatus main body such as a copying machine or a printer.
The process cartridge shown in FIG. 4 holds the electrostatic latent image after transferring it from the electrostatic latent image carrier (1), electrostatic latent image charging means (5), and electrostatic latent image carrier (1) to the next process. There are provided charging means (3) having a sheet pressure contact member (4) and developing means (6) for recharging the toner remaining on the surface of the body (1). In the figure, reference numeral (7) denotes a transfer means used for transferring the toner image to the transfer member (2).

The operation of the process cartridge will be described. The electrostatic latent image carrier is rotationally driven at a predetermined peripheral speed.
In the rotating process, the electrostatic latent image carrier (1) is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the charging means (5), and then an image such as slit exposure or laser beam scanning exposure (not shown). In response to the image exposure light from the exposure means, electrostatic latent images are sequentially formed on the peripheral surface of the electrostatic latent image carrier (1), and the formed electrostatic latent images are then developed by the developing means (6). The developed and developed toner image is fed from the paper feeding unit between the electrostatic latent image carrier (1) and the transfer means (7) in synchronization with the rotation of the electrostatic latent image carrier (1). The transfer means (7) sequentially transfers the transferred member (2).
The transfer member (2) that has received the image transfer is separated from the surface of the electrostatic latent image carrier, and is introduced into an image fixing means (not shown) to fix the image, and then is copied out (copy) or printed (print) out of the apparatus. Printed out. The surface of the electrostatic latent image carrier (1) after image transfer is transferred again from the electrostatic latent image carrier (1) to the toner remaining on the surface of the electrostatic latent image carrier (1) after transfer to the next step. The remaining toner after transfer is recharged by the charging means (3) for charging, passes through the electrostatic latent image carrier charging portion, is collected in the developing process, and is repeatedly used for image formation.

Next, a method for measuring physical properties of raw materials used in the examples will be described.
<Measurement of particle size of colored resin particles>
The volume average particle diameter of the colored resin particles is determined by a Coulter counter method. Examples of the measuring device include Coulter Counter TA-II, Coulter Multisizer II, and Coulter Multisizer III (all manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

<Measurement of particle size of resin fine particles to be attached to core surface>
The particle size of the resin fine particles was measured using UPA-150EX (manufactured by Nikkiso Co., Ltd.).

<Molecular weight measurement (GPC)>
The molecular weight of the resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
-Column: KF801-807 (manufactured by Shodex)-Temperature: 40 ° C
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
The number average molecular weight and weight average molecular weight of the resin were calculated from the molecular weight distribution of the resin measured under the above conditions using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. As standard polystyrene samples for preparing calibration curves, Showdex STANDARD's Std.No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

<Glass transition temperature (Tg) measurement (DSC)>
As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

<Acid value measurement>
The acid value of the resin is measured according to JIS K1557-1970. A specific measurement method is shown below.
About 2 g of the pulverized sample is precisely weighed (W (g)).
A sample is put into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved for 5 hours, and then a phenolphthalein solution is added as an indicator.
The solution is titrated with a burette using a 0.1 N potassium hydroxide alcohol solution. The amount of the KOH solution at this time is S (ml). A blank test is performed, and the amount of the KOH solution at this time is defined as B (ml).
The acid value is calculated by the following formula.
Acid value = [(SB) × f × 5.61] / W
(F: Factor of KOH solution)

<Measurement of hydroxyl value>
The sample is precisely weighed into a 100 ml eggplant flask, and 5 ml of acetylating reagent is correctly added thereto.
Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated.
After 1-2 hours, the flask is removed from the bath and allowed to cool, and then ion-exchanged water is added and shaken to decompose acetic anhydride.
Furthermore, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using a glass electrode to obtain a hydroxyl value (according to JIS K0070-1966).

<Measurement of solid content concentration>
Measurement of the solid content concentration of the oil phase was performed as follows.
On an aluminum pan (about 1 to 3 g) whose mass has been accurately weighed in advance, about 2 g of the oil phase is placed within 30 seconds, and the mass of the placed oil phase is accurately weighed. This is placed in an oven at 150 ° C. for 1 hour to evaporate the solvent, then taken out of the oven, allowed to cool, and the mass of the aluminum dish and the oil phase solids is measured with an electronic balance. Calculate the mass of the oil phase solid by subtracting the mass of the aluminum pan from the total mass of the aluminum pan and the oil phase solid content, and calculate the solid content concentration of the oil phase by dividing by the mass of the oil phase on which it is placed. . The ratio of the amount of the solvent to the solid content in the oil phase is a value obtained by dividing a value obtained by subtracting the mass of the oil phase solid content from the mass of the oil phase (mass of the solvent) by the mass of the oil phase solid content.

[Production of resin fine particle dispersion 1]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution obtained by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 4.2 parts of n-octanethiol was dropped over 90 minutes, Thereafter, the polymerization reaction was carried out at 80 ° C. for another 60 minutes.
Then, it cooled and the white resin fine particle dispersion liquid 1 with a volume average particle diameter of 105 nm was obtained.

[Production of resin fine particle dispersion 2]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution of 2.6 parts dissolved in 105 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 12 parts of butyl acrylate, 18 parts of methacrylic acid, and 4.2 parts of n-octanethiol. The mixed solution was added dropwise over 90 minutes, and then the polymerization reaction was further maintained at 80 ° C. for 60 minutes. Then, it cooled and the white resin fine particle dispersion liquid 2 with a volume average particle diameter of 120 nm was obtained.

[Production of resin fine particle dispersion 3]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution prepared by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 140 parts of styrene monomer and 60 parts of methoxydiethylene glycol methacrylate was added dropwise over 90 minutes, and then another 60 parts. The polymerization reaction was carried out by maintaining the temperature at 80 ° C. for a minute. Then, it cooled and the white resin fine particle dispersion liquid 3 with a volume average particle diameter of 115 nm was obtained.

[Production of resin fine particle dispersion 4]
In a 5 liter stainless steel kettle, 1500 g of [Linear Polyester 1] described later, anionic surfactant “Neopelex G-15 (manufactured by Kao)” [Sodium dodecylbenzenesulfonate (solid content: 15% by weight)] 100 g, 15 g of nonionic surfactant “Emulgen 430 (manufactured by Kao Corporation)” [polyoxyethylene (26 mol) oleyl ether (HLB: 16.2)], and 689 g of 5 wt% aqueous potassium hydroxide solution And dispersed at 25 degrees with stirring at 200 r / min.
The contents were stabilized at 95 degrees and held for 2 hours under stirring at 200 r / min with a chi-type stirrer.
Subsequently, deionized water was added dropwise at 15 g / min while stirring at 200 r / min with a Kai-type stirrer, and a total of 2845 g was added.
Further, the temperature in the system was maintained at 95 degrees while deionized water was added dropwise.
Then, it cooled and the white resin fine particle dispersion 4 with a volume average particle diameter of 150 nm was obtained.

[Production of resin fine particle dispersion 5]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.6 part of sodium dodecyl sulfate and 466 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring, and then potassium persulfate is added. 2 parts dissolved in 81 parts of ion-exchanged water were added, and 15 minutes later, 140 parts of styrene monomer, 20 parts of butyl acrylate, 40 parts of polyester, and 1.8 parts of n-octanethiol Was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction.
Then, it cooled and the white resin fine particle dispersion 5 with a volume average particle diameter of 108 nm was obtained.

[Production of resin fine particle dispersion 6]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 1.4 parts of sodium dodecyl sulfate and 498 parts of ion-exchanged water were dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution obtained by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 4.2 parts of n-octanethiol was dropped over 90 minutes, Thereafter, the polymerization reaction was carried out at 80 ° C. for another 60 minutes.
Then, it cooled and the white resin fine particle dispersion liquid 6 with a volume average particle diameter of 65 nm was obtained.

[Production of resin fine particle dispersion 7]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1.0 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution obtained by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 4.2 parts of n-octanethiol was dropped over 90 minutes, Thereafter, the polymerization reaction was carried out at 80 ° C. for another 60 minutes.
Then, it cooled and the white resin fine particle dispersion liquid 7 with a volume average particle diameter of 95 nm was obtained.

[Synthesis of linear polyester 1]
270 parts of bisphenol A ethylene oxide 2-mole adduct, 497 parts of bisphenol A propylene oxide 2-mole adduct, 110 parts of terephthalic acid, 102 parts of isophthalic acid, adipic acid 44 parts and 2 parts of dibutyltin oxide were charged and reacted at 230 ° C. for 9 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 18 mmHg for 7 hours, 40 parts of trimellitic anhydride is added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure. [Linear polyester 1] Was synthesized. The obtained [Linear Polyester 1] had a number average molecular weight of 3000, a weight average molecular weight of 8600, a glass transition temperature of 49 ° C., and an acid value of 22 mgKOH / g.

[Synthesis of linear polyester 2]
In a reaction vessel equipped with a cooling tube stirrer and a nitrogen introduction tube, 218 parts of bisphenol A ethylene oxide 2-mole adduct, 460 parts of bisphenol A propylene oxide 2-mole adduct, 140 parts of terephthalic acid, 145 parts of isophthalic acid, and dibutyltin 2 parts of oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 18 mmHg for 6 hours, 24 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. [Linear polyester 2] Was synthesized. The obtained [Linear Polyester 2] had a number average molecular weight of 7600, a weight average molecular weight of 21,000, a glass transition temperature of 57 ° C., and an acid value of 15 mgKOH / g.

[Synthesis of linear polyester 3]
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 2-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, and dibutyltin in a reaction vessel equipped with a condenser and a nitrogen introducing tube 2 parts of oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting for 5 hours under a reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure. [Linear polyester 3] Was synthesized.
The obtained [Linear Polyester 3] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

[Prepolymer synthesis]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polyester [Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 350 parts of bisphenol A / EO 2 mol adduct, 326 parts of bisphenol A / PO 3 mol adduct, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and polycondensation 1.5 parts of potassium titanyl oxalate was added as a catalyst, and the reaction was carried out at 230 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain a non-linear polyester resin.
The non-linear polyester resin contained no THF-insoluble matter, and had an acid value of 35, a hydroxyl value of 17, a Tg of 69 ° C., a number average molecular weight of 3800, and a weight average molecular weight of 56,000.

[Manufacture of master batch 1]
Carbon black: 40 parts, polyester 1:60 parts, and water: 30 parts were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 & ° C. and pulverized to a size of 1 mm with a pulverizer to obtain [Masterbatch 1].

[Example 1]
<Water phase preparation process>
948 parts of ion-exchanged water, 42 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether When 120 parts of a 48.5% aqueous solution of sodium disulfonate and 90 parts of ethyl acetate were mixed and stirred, the pH reached 6.1. A 10% aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH to 12.5 to obtain [Aqueous Phase 1].

<Oil phase preparation process>
545 parts of [Linear Polyester 1], 181 parts of [paraffin wax (melting point 74 ° C.)] and 1450 parts of ethyl acetate are charged in a container equipped with a stir bar and a thermometer. This was maintained for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 655 parts of a 66% ethyl acetate solution of [Linear Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1].
[Pigment / WAX Dispersion 1] 976 parts were mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), and then 88 parts of [Prepolymer 1] were added to a TK homomixer (tokushu Tokukai). Was mixed at 5,000 rpm for 1 minute to obtain [Oil Phase 1]. The solid content of [Oil Phase 1] obtained was measured to be 52.0% by weight, and the amount of ethyl acetate based on the solid content was 92% by weight.

<Core particle production process>
Add 1200 parts of [Aqueous Phase 1] to the obtained [Oil Phase 1], and cool in a water bath to suppress the temperature rise due to shear heat of the mixer so that the temperature in the liquid is in the range of 20-23 ° C. Adjusting to 4,000 to 12,000 rpm using a TK homomixer and mixing for 3 minutes, adjusting to 200 to 600 rpm with a three-one motor with an anchor blade attached for 10 minutes The mixture was stirred to obtain [core particle slurry 1] in which oil phase droplets serving as core particles were dispersed in an aqueous phase.

<Resin fine particle adhesion process>
While the [core particle slurry 1] is adjusted with a three-one motor attached with an anchor blade between 200 to 600 rpm and stirred, the liquid temperature is 22 ° C. and 106 parts of [resin fine particle dispersion 1] and ions What mixed 71 parts of exchange water (solid content concentration 15%) was dripped over 3 minutes. After the dropping, the rotation speed was maintained between 200 and 600 rpm and stirring was continued for 30 minutes to obtain [Composite Particle Slurry 1]. When 1 ml of this [Composite Particle Slurry 1] was taken and diluted to 10 ml and centrifuged, the supernatant was “clear”.

<Demelting process>
[Composite particle slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 1]. When [Dispersion Slurry 1] was placed on a small amount of slide glass and observed with an optical microscope at a magnification of 200 times with a cover glass in between, uniform colored particles were observed. Further, when 1 ml of [Dispersion Slurry 1] was taken and diluted to 10 ml and centrifuged, the supernatant was “transparent”.

<Washing and drying process>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh opening of 75 μm, [Colored resin particles 1] (volume average particle diameter (Dv) was 6.8 μm, Dv / Dn was 1.15) was obtained. When the obtained [colored resin particle 1] was observed with a scanning electron microscope, the resin fine particles were uniformly attached to the surface of the core particle.

[Example 2]
<Preparation of pigment / WAX dispersion (oil phase)>
In a container equipped with a stir bar and a thermometer, 175 parts of [non-linear polyester resin], 430 parts of [linear polyester 1], 153 parts of [paraffin wax (melting point 74 ° C.)] and 1450 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 410 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Material solution 2].
[Raw material solution 2] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 470 parts of a 70% ethyl acetate solution of [Linear Polyester 1], 250 parts of a 55% ethyl acetate solution of [Linear Polyester 1], and 95 parts of ethyl acetate were added, and the oil phase was passed through one pass with a bead mill under the above conditions. As a result, [Pigment / WAX Dispersion 2] was obtained. The solid content of the obtained [Pigment / WAX Dispersion 2] was measured to be 49.3% by weight, and the amount of ethyl acetate based on the solid content was 103% by weight.
<Core particle production process>
[Pigment / WAX Dispersion 2], 976 parts, was mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), and then added at 5,000 rpm with a TK homomixer (made by Tokushu Kika). After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added and mixed for 3 minutes while adjusting at 4,000 to 12,000 rpm with a TK homomixer to obtain [Core Particle Emulsion Slurry 2].

<Resin fine particle adhesion process>
While the [core particle slurry 2] is adjusted with a three-one motor attached with an anchor blade between 200 to 600 rpm and stirred while the liquid temperature is 22 ° C., 106 parts of [resin fine particle dispersion 1] and ions What mixed 71 parts of exchange water (solid content concentration 15%) was dripped over 3 minutes. After the dropping, the number of rotations was adjusted to 200 to 600 rpm, and stirring was continued for 30 minutes to obtain [Composite Particle Slurry 4]. When 1 ml of [Composite Particle Slurry 4] was taken and diluted to 10 ml and centrifuged, the supernatant was “almost transparent”.

<Demelting process>
[Composite particle slurry 2] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 2]. [Dispersion slurry 2] was placed on a small amount of slide glass, and the state was observed at 200 times magnification with an optical microscope with a cover glass interposed therebetween, and uniform colored particles were observed. When 1 ml of [Dispersion Slurry 2] was taken and diluted to 10 ml and centrifuged, the supernatant was “almost transparent”.

<Washing and drying process>
[Dispersion slurry 2] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 2].
[Filter cake 2] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh opening of 75 μm. [Colored resin particles 2] (volume average particle diameter (Dv) was 6.9 μm, Dv / Dn was 1.17) was obtained. When the obtained [colored resin particle 2] was observed with a scanning electron microscope, the resin fine particles were uniformly attached to the surface of the core particle.

[Example 3]
Colored fine particles were obtained in the same manner as in Example 1 except that there was no acid treatment in the washing step.
[Example 4]
In the aqueous phase preparation step, colored fine particles were obtained in the same manner as in Example 1 except that a 10% aqueous potassium hydroxide solution was used instead of the 10% aqueous sodium hydroxide solution.
[Example 5]
In the aqueous phase preparation step, colored fine particles were obtained in the same manner as in Example 2 except that a 10% aqueous potassium hydroxide solution was used instead of the 10% aqueous sodium hydroxide solution.
[Example 6]
Colored fine particles were obtained in the same manner as in Example 1 except that the resin fine particle dispersion 1 attached to the surface of the core particle slurry was changed to the resin fine particle dispersion 2.
[Example 7]
Colored fine particles were obtained in the same manner as in Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 2.

[Example 8]
Colored fine particles were obtained in the same manner as in Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 3.
[Example 9]
Colored fine particles were obtained in the same manner as in Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 3.
[Example 10]
Colored fine particles were obtained in the same manner as in Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 4.
[Example 11]
Colored fine particles were obtained in the same manner as in Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 4.
[Example 12]
Colored fine particles were obtained in the same manner as in Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 5.

[Example 13]
Colored fine particles were obtained in the same manner as in Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 5.
[Example 14]
Colored fine particles were obtained in the same manner as in Example 1 except that the linear polyester 1 used in the oil phase preparation was replaced with the linear polyester 2.
[Example 15]
Colored fine particles were obtained in the same manner as in Example 2 except that the linear polyester 1 used in the oil phase preparation was replaced with the linear polyester 2.
[Example 16]
Colored fine particles were obtained in the same manner as in Example 1 except that the linear polyester 1 used in the oil phase preparation was replaced with the linear polyester 3.
[Example 17]
Colored fine particles were obtained in the same manner as in Example 2 except that the linear polyester 1 used in the oil phase preparation was replaced with the linear polyester 3.

[Example 18]
In Example 1, colored fine particles were obtained in the same manner as in Example 1 except that the 10% aqueous sodium hydroxide solution added to the aqueous phase was added to [Pigment / WAX Dispersion 1].
[Example 19]
In Example 2, colored fine particles were obtained in the same manner as in Example 2 except that the 10% aqueous sodium hydroxide solution added to the aqueous phase was added to [Pigment / WAX Dispersion 1].
[Example 20]
Colored fine particles were obtained in the same manner as in Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 6.

[Example 21]
Colored fine particles were obtained in the same manner as in Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 6.
[Example 22]
Colored fine particles were obtained in the same manner as in Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 7.
[Example 23]
Colored fine particles were obtained in the same manner as in Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 7.

[Example 24]
<Water phase preparation process>
948 parts of ion-exchanged water, 45 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether When 112 parts of a 48.5% aqueous solution of sodium disulfonate was mixed and stirred, the pH reached 5.8. A 25% aqueous ammonia solution was added dropwise thereto to adjust the pH to 9.8. To this, 90 parts of ethyl acetate was added and mixed and stirred to obtain [Aqueous Phase 24].
Hereinafter, [Colored resin particles 24] (volume average particle diameter (Dv) is 6.9 μm, Dv / Dn is the same as in Example 1 except that [aqueous phase 24] is used instead of [aqueous phase 1]. 1.16) was obtained. When the obtained [colored resin particles 24] were observed with a scanning electron microscope, the resin fine particles were uniformly attached to the surfaces of the core particles.

[Comparative Example 1]
<Oil phase preparation process>
545 parts of [Linear Polyester 1], 181 parts of [paraffin wax (melting point 74 ° C.)] and 1450 parts of ethyl acetate are charged in a container equipped with a stir bar and a thermometer. This was maintained for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 101].
[Raw material solution 101] 1500 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec, 0.5 mm zirconia beads 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 655 parts of a 65% ethyl acetate solution of [Linear Polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 101] as an oil phase. Ethyl acetate was added to adjust the solid content concentration of [Pigment / WAX Dispersion 101] (130 ° C., 30 minutes) to 50%.
[Pigment / WAX Dispersion 101] 976 parts and Isophoronediamine 2.5 parts were mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), then 88 parts of [Prepolymer 1] were added and TK homopolymer was added. [Oil phase 101] was obtained by mixing for 1 minute at 5,000 rpm with a mixer (manufactured by Tokushu Kika). In terms of the charged amount, the solid content concentration of [Oil Phase 1] is 50% by weight, and the amount of ethyl acetate with respect to the solid content is 100% by weight. When the solid content of the obtained [Oil Phase 101] was actually measured, it was 52% by weight, and the amount of ethyl acetate based on the solid content was 92% by weight.
Colored fine particles were obtained in the same manner as in Example 1 except that [Oil phase 101] was used and 10% sodium hydroxide was not used in the aqueous phase.

[Comparative Example 2]
<Preparation of pigment / WAX dispersion (oil phase)>
In a container equipped with a stir bar and a thermometer, 175 parts of [non-linear polyester resin], 430 parts of [linear polyester 1], 153 parts of [paraffin wax (melting point 74 ° C.)] and 1450 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 410 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 102].
[Raw material solution 102] 1500 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 470 parts of a 70% ethyl acetate solution of [Linear Polyester 1], 250 parts of a 55% ethyl acetate solution of [Linear Polyester 1] and 95 parts of ethyl acetate were added, and one pass was performed with a bead mill under the above conditions. Phase 102] was obtained. The solid content of the obtained [oil phase 102] was measured to be 49.4% by weight, and the amount of ethyl acetate based on the solid content was 102% by weight.
[Pigment / WAX dispersion 102] 976 parts and 3.0 parts of isophoronediamine were mixed with a TK homomixer (manufactured by Tokushu Kika) for 1 minute at 5,000 rpm, and then added to a TK homomixer (tokushu Tokushu Kika). ) At 5,000 rpm for 1 minute, add 1200 parts of [preliminary solid phase and Ph-adjusted aqueous phase], and mix for 3 minutes while adjusting at 4,000 to 12,000 rpm with a TK homomixer. Then, colored fine particles were obtained in the same manner as in Example 2 except that [core particle emulsified slurry 102] was obtained.

[Comparative Example 3]
Colored fine particles were obtained in the same manner as in Comparative Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 2.
[Comparative Example 4]
Colored fine particles were obtained in the same manner as in Comparative Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 2.
[Comparative Example 5]
Colored fine particles were obtained in the same manner as in Comparative Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 3.

[Comparative Example 6]
Colored fine particles were obtained in the same manner as in Comparative Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 3.
[Comparative Example 7]
Colored fine particles were obtained in the same manner as in Comparative Example 1 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 4.
[Comparative Example 8]
Colored fine particles were obtained in the same manner as in Comparative Example 2 except that the resin fine particle dispersion 1 adhered to the surface of the core particle slurry was changed to the resin fine particle dispersion 4.

[Comparative Example 9]
Colored fine particles were obtained in the same manner as in Comparative Example 1 except that the amount of isophoronediamine added dropwise to the pigment / WAX dispersion was changed from 2.5 parts to 2.0 parts.
[Comparative Example 10]
Colored fine particles were obtained in the same manner as in Comparative Example 2 except that the amount of isophoronediamine added dropwise to the pigment / WAX dispersion was changed from 3.0 parts to 2.5 parts.
[Comparative Example 11]
Colored fine particles were obtained in the same manner as in Comparative Example 1 except that the amount of isophoronediamine added dropwise to the pigment / WAX dispersion was changed from 2.5 parts to 3.0 parts.
[Comparative Example 12]
Colored fine particles were obtained in the same manner as in Comparative Example 2 except that the amount of isophoronediamine added dropwise to the pigment / WAX dispersion was changed from 3.0 parts to 3.5 parts.

Analysis and evaluation in the case where the colored resin particles of Examples 1 to 23 and Comparative Examples 1 to 12 prepared above were used as toners were performed as follows.
The evaluation results are shown in Table 1.
In Table 1, “With ester extension reaction” in the column of method indicates that a method involving a prepolymer extension / crosslinking reaction (ester extension polymerization), which is one of the dissolution suspension methods, was used as the method. . More specifically, as in Example 1, when the end-modified isocyanate-modified polyester is dissolved in an organic solvent together with unmodified polyester and dispersed in an aqueous dispersion, the toner is subjected to an isocyanate extension reaction. A method of granulating particles.

<Adhering to regulation blade>
Using Ricoh's ipsio SP C220, the state of the developing roller of the developer after a predetermined print pattern with a printing rate of 6% after continuous copying (after endurance) of 2000 sheets in an N / N environment (23 ° C, 45%) The copied images were visually observed and evaluated. Judgment criteria are as follows.
○: No streak or unevenness occurred on the developing roller.
Δ: Although some streaks or unevenness occurred on the developing roller, there were no vertical streaks on the copied image, and there was no practical problem.
X: Many streaks or unevenness occurred on the developing roller, and vertical streak-like omission occurred on the copied image, which had a problem in practical use.
“◯” and “△” were accepted.

<Photoconductor ground stain>
Using Ricoh's ipsio SP C220, a predetermined print pattern with a printing rate of 6% can be printed in an N / N environment (23 ° C., 45%) at the beginning (before durability) and after 2000 continuous copying (after durability). The L * of the background toner was determined by a tape transfer method. The tape transfer method is a method in which a mending tape (manufactured by Sumitomo 3M) is affixed onto the toner existing on the photoconductor to transfer fog toner onto the tape. This is a method of pasting each on white paper, measuring the reflection density with X-Rite 939, and obtaining the difference L * as the reflection density of the background stain.
○: Change rate of L * after initial and endurance is within 2%
Δ: Change rate of L * between the initial stage and after endurance is within 2% to 5%
X: The rate of change in L * after the initial stage and after endurance was 5% or more.

<Supernatant evaluation rank>
The determination as to whether the fine resin particles are attached to the core agent is based on the transparency of the supernatant of the fine resin particles by a centrifuge as an evaluation method. Described below.
1 ml of the composite particle slurry in which resin fine particles were dropped into the core particle slurry was taken and diluted to 10 ml, centrifuged, and the following five-stage visual liquid was prepared and visually ranked.
A: The supernatant liquid was “transparent”.
○: The supernatant liquid was “almost transparent”.
Δ: The supernatant liquid was “slightly cloudy”.
X; The clear solution was “substantially cloudy”.
XX: The supernatant was “completely cloudy”.

  The colored resin particle manufacturing method of the present invention can efficiently and uniformly deposit resin fine particles on the core particle without going through a heating step, and can be manufactured with less manufacturing environmental load. It is suitable as a method for producing colored resin particles for image formation of toner for electronic use and electronic paper.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Image formation part 3 Charging device (charging roller)
4 exposure device 5 developing device 5a developing roller 5b developer supply roller 5c regulating blade 6 transfer device 7 cleaning device 10 intermediate transfer belt 11, 12, 13 support roller 14 (14Y, 14C, 14M, 14K): primary transfer roller 15 belt Cleaning device 16 Secondary transfer roller 20: Paper feed cassette 21: Paper feed roller 22: Registration roller pair 23: Heat fixing device (fixing means)
24: paper discharge roller 30: color image forming unit 31Y, 31C, 31M, 31K: toner bottle T toner (developer)

JP 2006-208551 A JP 2006-285188 A JP 2008-208354 A

Claims (12)

Producing an oil phase in which at least a resin and a colorant are dissolved or dispersed in an organic solvent;
Producing an aqueous phase having at least a surfactant in an aqueous medium;
A step of dispersing the oil phase in the aqueous phase to produce a colored particle dispersion to produce core particles;
Adding at least resin fine particles to the colored particle dispersion in which the core particles are formed, and attaching the resin fine particles to the surface of the core particles;
Removing the solvent to obtain colored resin particles;
Washing the colored resin particles;
In the method for producing colored resin particles including at least a step of drying the colored resin particles, an inorganic base is dissolved in the colored particle dispersion to be alkaline , and a heating step is performed in the step of attaching the resin fine particles. A method for producing colored resin particles, characterized by not passing through .   The method for producing colored resin particles according to claim 1, wherein the inorganic base is added in a step of producing the aqueous phase or a step of producing an oil phase in which the colorant is dissolved or dispersed.   3. The method for producing colored resin particles according to claim 1, wherein the resin fine particles have a volume average particle diameter of 60 to 120 nm.   The method for producing colored resin particles according to claim 1, wherein the washing step is a washing treatment with an acid.   The method for producing colored resin particles according to any one of claims 1 to 4, wherein the acid value of the resin is 2 to 26 mgKOH / g.   The method for producing colored resin particles according to claim 1, wherein the resin is a polyester resin.   The method for producing colored resin particles according to any one of claims 1 to 6, wherein a modified resin having an isocyanate group at a terminal is dissolved in the oil phase.   The method for producing colored resin particles according to claim 7, wherein the modified resin has a polyester skeleton.   The method for producing colored resin particles according to claim 1, wherein the resin fine particles are made of a vinyl resin.   The method for producing colored resin particles according to claim 9, wherein a styrene monomer contained in the vinyl resin is 80% by weight or more.   The method for producing colored resin particles according to claim 10, wherein a styrene monomer contained in the vinyl resin is 90% by weight or more.   The method for producing colored resin particles according to any one of claims 1 to 11, wherein the colored resin particles do not contain an amine compound having an active hydrogen group.

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